Deodorant and cosmetic shampoo preparation containing the same

ABSTRACT

A deodorant which is suitable for removal of various odors in daily life, especially for removing a chemical odor remaining in the hair after a permanent wave treatment. It less irritates the hair and skin and is suitable for incorporation into a shampoo, treatment agent, etc. The deodorant contains a deodorizing ingredient selected among the following (a) to (d): (a) a hydroxy acid salt of a divalent metal (b) a fatty acid salt of a divalent metal (c) an oxide of a divalent metal and a hydroxy acid, fatty acid, or chelating agent (d) an inorganic acid salt of a divalent metal and a hydroxy acid, fatty acid, or chelating agent.

TECHNICAL FIELD

This invention relates to a deodorant. More particularly the presentinvention is a deodorant that works against various basic odors (such asammonia) and acidic odors (such as mercaptans), and is used to eliminatedaily odors such as body odor, excrement odor, and other indoor odors.The deodorant of the present invention is particularly effective atremoving the unpleasant odors of chemical agents that remain behindafter head hair has undergone a permanent wave treatment. The presentinvention also relates to a head hair washing product, and particularlya shampoo or treatment agent (rinse), containing the above-mentioneddeodorant. The deodorant of the present invention also has anantibacterial action.

BACKGROUND ART

As the standard of living here [in Japan] has risen, there has beengrowing interest in environmental sanitation and in preventing andeliminating odors. Methods known in the past for reducing malodorousingredients included masking unpleasant odors with a powerful perfume;physical methods such as adsorbing odors with activated charcoal,alumina, zeolite, or another such porous adsorbent; chemical methodssuch as catalytic combustion, oxidation of the odor ingredients withozone, and neutralization with chemicals; and biochemical methods suchas decomposing odor ingredients with bacteria.

For example, when head hair is subjected to a permanent wave treatmentat a beauty salon or the like, ammonium thioglycolate and other suchchemicals are used to make the wave last longer. Almost all of thechemical is removed upon completion of the permanent treatment byrinsing with water or performing an acid treatment (pH of about 3) orreduction treatment. Nevertheless, a tiny amount of ammoniumthioglycolate ingredient remains on the head hair, and this leaves thehead hair with a distinctive odor for 2 to 3 days.

Unpleasant odors that actually pose a problem in daily life, such as theresidual odor after a permanent treatment, include basic odors, acidicodors, and odors that are a mixture of these, and are made up of avariety of ingredients. There is a need for a deodorant that iseffective against all of these unpleasant odor ingredients.

It is an object of the present invention to provide a deodorant that issuited to the removable of various odors encountered in daily life, andespecially the chemical smell that remains on head hair after apermanent wave treatment. The inventor conducted various investigationsaimed at solving this problem. As a result, the inventor learned thatusing a deodorizing antibacterial agent comprising a combination of adivalent metal ion such as a copper ion and a hydroxy acid, a fatty acidor another such organic acid ingredient, or a specific chelating agentallows odors after a permanent treatment to be effectively eliminated,and causes minimal irritation to the head hair and skin.

DISCLOSURE OF THE INVENTION

The first invention of the present application is a deodorant containinga deodorizing ingredient selected from among the following (a) to (d):

-   -   (a) a hydroxy acid salt of a divalent metal    -   (b) a fatty acid salt of a divalent metal    -   (c) an oxide of a divalent metal and a hydroxy acid, fatty acid,        or chelating agent    -   (d) an inorganic acid salt of a divalent metal and a hydroxy        acid, fatty acid, or chelating agent.

These divalent metals are preferably copper, zinc and/or iron. Thesecond invention of the present application is a head hair washingproduct such as a shampoo or treatment agent containing the deodorant.The third invention of the present application is a head hair treatmentmethod, wherein the head hair is first given a permanent wave, and thenwashed using the head hair washing product. The fourth invention of thepresent application is a deodorizing antibacterial substrate, producedby applying the deodorant to the surface and/or the interior of afibrous material, granular material, paper, nonwoven cloth, woven cloth,porous substance, or polymer film. The deodorant may further contain abetaine compound, a carbonyl compound, and/or α-olefin/maleic anhydridecopolymer.

BEST MODE FOR CARRYING OUT THE INVENTION DETAILED DESCRIPTION OF THEINVENTION

The active ingredient in the deodorant of the present invention againstacidic odors such as amines and mercaptans is believed to be a divalentmetal ion. The active ingredient against basic odors such as ammonia inthis deodorant is believed to be a hydroxy acid radical, fatty acidradical, or the like.

(a) Metal Compound

The divalent metal ion can be introduced in any of various forms, but inparticular it can be introduced as a divalent metal oxide, inorganicmetal salt (such as a sulfate), or organic acid salt (such as a hydroxyacid metal salt or fatty acid metal salt). These divalent metal ions aremainly capable of eliminating amine odors, mercaptan odors, and othersuch acidic odors.

The amount in which the metal compound is contained in the deodorant maybe suitably selected according to the form of the deodorant, but isusually 0.01 to 30 wt %, and preferably 0.1 to 5 wt %, with respect tothe total amount of deodorant. In a head hair washing product, [thiscontent] is 0.01 to 10 wt %, and preferably 0.05 to 5 wt %.

Metal Oxide

Examples of metal oxides that can be used in the deodorizingantibacterial agent of the present invention include metal oxides thatprovide divalent metal ions in a solution in the presence of a hydroxyacid or fatty acid such as copper oxide, zinc oxide, and iron oxide.

Inorganic Metal Salt

Examples of inorganic salts of divalent metals that can be used in thedeodorizing antibacterial agent of the present invention includesulfates and nitrates. Specific examples include copper sulfate, coppernitrate, zinc sulfate, and iron sulfate. These provide divalent metalions in a solution in the presence of a hydroxy acid or fatty acid.

Hydroxy Acid Metal Salt

Of the various organic acid salts, examples of hydroxy acid metal saltsinclude hydroxy acid copper salts, hydroxy acid zinc salts, and hydroxyacid iron salts. Examples of the hydroxy acid ingredient of thesehydroxy acid metal salts include gluconic acid and other such aldonicacids, as well as saccharic acid and other such saccharide oxides, andvarious other hydroxy acids such as ascorbic acid, dehydroascorbic acid,lactic acid, malic acid, tartaric acid, citric acid, glycolic acid,hydroxybenzoic acid, gallic acid, mandelic acid, and tropic acid. Ofthese, gluconic acid, malic acid, and citric acid are preferable, andgluconic acid is particularly favorable. Therefore, copper gluconate andzinc gluconate are preferred.

A commercially available hydroxy acid metal salt can be used, but acombination of a hydroxy acid such as gluconic acid, saccharic acid, orascorbic acid and one of the above-mentioned metal oxides (such ascopper oxide, zinc oxide, and iron oxide) or an inorganic metal salt maybe used instead. When a hydroxy acid ingredient is thus present, itstabilizes the divalent metal ion, yielding a higher metal ionconcentration. The hydroxy acid metal salts may be used singly or incombinations of two or more types.

Gluconic acid metal salts such as copper gluconate and zinc gluconatehave good deodorizing action against unpleasant odors from both ammoniaand mercaptans, and give an excellent deodorant and antibacterial agent.

Fatty Acid Metal Salt

Of the various organic acid salts, the fatty acid metal salts can bemetal salts of saturated or unsaturated fatty acids with 1 to 30carbons. Specific favorable examples include metal salts of saturatedfatty acids such as acetic acid, propionic acid, undecylenic acid,palmitic acid, lauric acid, myristic acid, palmitic acid [sic], stearicacid, and behenic acid; and of unsaturated fatty acids such as oleicacid, sorbic acid, linoleic acid, linolenic acid, ricinoleic acid, andarachidonic acid. Examples of these metal salts include zinc, copper,iron, molybdenum, cobalt, aluminum, titanium, manganese, nickel, andsilver, with copper, zinc, and iron salts being particularly preferred.

A commercially available fatty acid metal salt can be used, but acombination of a fatty acid such as palmitic acid or stearic acid andone of the above-mentioned metal oxides (such as copper oxide, zincoxide, and iron oxide) or an inorganic metal salt may be used instead.This fatty acid metal salt exhibits an excellent deodorizing actionagainst basic and acidic odors from ammonia, mercaptans, and so forth.These fatty acid metal salts may be used singly or in combinations oftwo or more types.

Chelating Agent

The chelating agent is preferably an amino acid type of chelating agent,and specific examples include hydroxyethylethylenediamine triacetate,ethylenediamine tetraacetate, nitrilotriacetate, diethylenetriaminepentaacetate, triethylenetetraamine hexaacetate, tetrasodiumdicarboxymethylglutamate, and dihydroxyethylglycine and the like. Withthe present invention, adding a chelating agent allows the metalcomponent concentration in the deodorant to be kept high in thesolution. The amount in which this agent is contained is 0.1 to 50weight parts, and preferably 1 to 20 [weight parts], weight parts per100 weight parts of deodorant.

(b) Betaine Acid

With the deodorant of the present invention, it is preferable to use abetaine compound along with the above-mentioned deodorizing ingredientin order to enhance the contact efficiency with the odor ingredient andto improve solubility in a solution of the deodorizing ingredient.Examples of such betaines include cocoamidopropyl betaine,2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine,2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine,lauryldimethylaminoacetic acid betaine,N-lauroyl-N-carboxymethyl-N-hydroxyethylimidazolinium, lauricacid-amidopropyl betaine, and various other betaines. The amount inwhich this betaine is contained is 10 to 300 weight parts, andpreferably 40 to 200 weight parts, per 100 weight parts of deodorizingingredient.

(c) Carbonyl Compound

A ketocarboxylic acid, aldehydic acid, or other such carbonyl compoundmay be further contained with the present invention. Examples of thiscarbonyl compound include glyceraldehyde, pyruvic acid, levulinic acid,aldehyde nonanoic acid, glyoxylic acid, and aldehydic acid. Adding thiscompound improves the removal of basic and acidic odors.

The amount in which this carbonyl compound is contained is 5 to 100weight parts, and preferably 10 to 200 weight parts, per 100 weightparts of gluconic acid metal salt or other deodorizing ingredient.

(d) α-Olefin/Maleic Anhydride Copolymer

The deodorant of the present invention may further contain anα-olefin/maleic anhydride copolymer in order to improve the removal ofbasic and acidic odors. Examples of such resins include methyl vinylether/maleic anhydride copolymers and isobutylene/maleic anhydridecopolymers. Typical examples of methyl vinyl ether/maleic anhydridecopolymers include products of various molecular weight available fromDaicel Chemical Industries under the product name of VEMA (an alternatecopolymer of methyl vinyl ether and maleic anhydride). Typical examplesof the above-mentioned isobutylene/maleic anhydride copolymers includeproducts of various molecular weight available from Kuraray Co., Ltd.under the product name of Isobam (an alternate copolymer of isobutyleneand maleic anhydride).

A reaction product obtained by reacting one of these α-olefin/maleicanhydride copolymers with a copper compound (such as copper oxide)and/or a zinc compound (such as zinc oxide) or the like may also beadded. Copper, zinc, or another such metal is bonded to at least some ofthe maleic anhydride structural units in this copolymer. The amount inwhich this copolymer is contained is 1 to 300 weight parts, andpreferably 5 to 100 weight parts, per 100 weight parts of gluconic acidmetal salt or other deodorizing ingredient.

The deodorant of the present invention exhibits excellent adsorptionpower and deodorizing effect against residual odors after a permanenttreatment, as well as ammonia or other such basic odors and mercaptansor other such acidic odors that pose a problem in daily life.Furthermore, if a betaine, fatty acid metal salt, inorganic metalcompound, carbonyl compound, or the like is added, substances that causeunpleasant odors, such as hydrogen sulfide and mercaptans, will beabsorbed even more effectively.

(Manufacturing Method)

In the manufacture of the deodorant of the present invention, a betaine,carbonyl compound, maleic anhydride copolymer, or the like can be usedas needed in liquid form, either dispersed or dissolved in a suitablesolvent, with the divalent metal compound such as a metal oxide,inorganic metal salt, or organic acid metal salt that serves as thedeodorizing ingredient.

There are no particular restrictions on the solvent used in thepreparation of the deodorant, as long as it will dissolve the variousingredients, but examples include water; alcohols such as methyl alcoholand ethyl alcohol; and dimethylformamide and dimethyl sulfoxide. Theamount in which the solvent is used is preferably 2 to 50 weight partsper 100 weight parts of deodorizing ingredient.

The deodorant of the present invention can be added to head hair washingproducts and various other head hair treatment products, such asshampoo, treatment agents, hair spray, hair milk, and blow-dryingagents, or can be added to other cosmetic products. To manufacture ahead hair treatment product or a head hair washing product such as ashampoo or treatment [agent], the above-mentioned deodorant should beadded to and mixed with known head hair washing product ingredients orhead hair treatment ingredients. In addition to the deodorant, thesehead hair washing agents and head hair treatment agents may containknown surfactants, perfumes, colorants, oils, antibacterial agents, andso forth according to the formulation of the product.

This deodorant may also be used to coat the surface of fibers or a film,or mixed into a film, for example, to deodorize the surroundingenvironment. Specifically, the deodorant of the present invention may beapplied as a layer over a substrate in any of various forms, such as asheet or yarn, or may be used to impregnate [such a substrate], whichincreases the surface area of the deodorant composition and improves itsdeodorizing action. This substrate can be nonwoven cloth, woven cloth, afibrous material such as yarn or monofilaments, a granular material,paper, or a porous substance such as zeolite, sepiolite, diatomaceousearth, or activated charcoal. These materials can be used singly or incombinations.

When the deodorant is applied to a substrate, various kinds of adhesivecolorant may also be added in order to adjust the hand or appearance ofthe product, or to apply an adhesive coating to a substrate composed ofa sheet- or yarn-form composition. A suitable polymer compound can beused as this substrate, examples of which include vinyl acetate/acryliccopolymers, polyvinyl alcohol, urethane resin, ethylene/vinyl acetatecopolymers, and carboxymethyl cellulose. These may be used singly or inmixtures.

In other usage modes of the deodorant of the present invention, it canbe dispersed and mixed into various polymer compounds, or it can bealternately dissolved into a base polymer to create a polymer blend, andthis mixture may be molded into a sheet, film, or the like.

EXAMPLES

The present invention will now be described in specific terms throughexamples. All added amounts in the examples and comparative examples arein weight percent.

Example 1

1.0 g of copper oxide and 5.0 g of ethylenediamine-tetraacetate (EDTA)were dispersed and stirred in enough water for the total to be 100 g.The deodorizing liquid thus obtained was sprayed onto tissue paper(10×10 cm) to impregnate the paper (adhering amount: 1 mL). This paperwas dried for 1 hour at 80° C. to obtain a deodorizing paper.

This deodorizing paper was placed in a Teflon® container (5 L volume),and nitrogen gas containing 5 L of ammonia (500 ppm) and 5 L of hydrogensulfide (100 ppm) was charged into the container. The change in gasconcentration in the container over time was measured, the results ofwhich are given in Table 1.

Examples 2 to 4

Other than preparing deodorants using the ingredients shown in Table 1,the various deodorants were manufactured in the same manner as inExample 1. Each was sprayed onto tissue paper to obtain deodorizingpaper. A deodorizing test was conducted in the same manner as in Example1, the results of which are given in Table 1. TABLE 1 Example 1 2 3 4copper oxide 1.0 — — 0.2 zinc oxide — 0.5 — — iron oxide — — 0.5 —copper sulfate — — — 2.0 ethylenediamine tetraacetate (EDTA) 5.0 — — —hydroxyethylethylenediamine triacetate — 7.0 — — nitrilotriacetate — —5.0 — triethylenetetraamine hexaacetate — — 1.5 — tetrasodiumdicarboxymethylglutamate — — 1.0 7.0 cocoamidopropyl betaine 10.0 10.010.0 5.0 purified water balance balance balance balance gasconcentration (ppm) NH₃ H₂S NH₃ H₂S NH₃ H₂S NH₃ H₂S after zero minute500 100 500 100 500 100 500 100 after thirty minutes 40 22 35 15 40 1520 15 after sixty minutes 5 3 1 2 2 1 2 1 after ninety minutes 0 0 0 0 00 0 0

Example 5

4.0 g of copper gluconate was dispersed and stirred in enough water forthe total to be 100 g. The deodorizing liquid thus obtained was sprayedonto tissue paper (10×10 cm) to impregnate the paper (adhering amount: 1mL). This paper was dried for 1 hour at 80° C. to obtain a deodorizingpaper. This deodorizing liquid^([6]) was placed in a Teflon® container(5 L volume), and nitrogen gas prepared to^([7]) 5 L of ammonia (500ppm) and 5 L of hydrogen sulfide (100 ppm), or these and 5 L of aceticacid (20 ppm), was charged into the container. The change in gasconcentration in the container over time was measured, the results ofwhich are given in Table 2.

Examples 6 to 14

Other than preparing deodorants using the ingredients shown in Tables 2and 3, the various deodorants were manufactured in the same manner as inExample 5. Each was sprayed onto tissue paper to obtain deodorizingpaper. The products were evaluated in the same manner as in Example 5,the results of which are given in Tables 2 and 3. TABLE 2 Example 5 6 78 9 10 11 Contrast copper gluconate 4.0 4.0 5.0 5.0 — 5.0 — — zincgluconate — — — — 5.0 — 5.0 — copper acetate — — — — — 5.0 — —cocoamidopropyl — 2.0 5.0 — — — — — betaine 2 alkyl-N- — — — 5.0 — — — —carboxymethyl-N- hydroxyethylimidazolinium betaine pyruvic acid — — — —— — 1.0 — purified water balance balance balance balance balance balancebalance balance gas concentration NH₃ H₂S NH₃ H₂S NH₃ H₂S acetic NH₃ H₂SNH₃ H₂S NH₃ H₂S NH₃ H₂S NH₃ H₂S (ppm) acid after zero minute 500 100 500100 500 100 20 500 100 500 100 500 100 500 100 500 100 after thirtyminutes 35 50 30 35 15 30 2 30 30 45 50 15 25 10 30 490 100 after sixtyminutes 2 5 5 8 0 2 0 5 10 10 15 0 5 0 5 490 100 after ninety minutes —— — — 0 0 0 0 0 1 5 0 0 0 0 490 100

TABLE 3 Example 12 13 14 copper oxide 0.5 — 0.5 zinc oxide — 0.2 —saccharic acid 5.0 — — gallic acid — — 4.0 ascorbic acid — 5.0 —cocoamidopropyl betaine — 10.0 10.0 purified water balance balancebalance gas concentration (ppm) NH₃ H₂S NH₃ H₂S NH₃ H₂S after zerominute 500 100 500 100 500 100 after thirty minutes 30 25 35 20 25 40after sixty minutes 1 2 5 2 5 10 after ninety minutes 0 0 0 0 0 0

Example 15 Shampoo

Deodorant composition wt % copper gluconate 52-alkyl-N-carboxymethyl-N-hydroxyethyl- 10 imidazolinium betaine pyruvicacid 1 purified water balance

Shampoo ingredients wt % triethanolamine alkylsulfate 25 polyoxyethylenealkyl (12, 13) ether 15 sodium sulfate coconut oil fatty aciddiethanolamide 5 table salt 1 propylene glycol 5 purified water balance

The above ingredients were mixed and stirred to prepare a deodorant anda shampoo base. Next, 2.5 g of the deodorant was added to 97.5 g of thisshampoo base to prepare a deodorant-containing shampoo. This shampoo wasused for the final head hair washing after an ordinary permanenttreatment (including an ammonium thioglycolate treatment). Aftershampooing, an organoleptic test was conducted to determine whether anyammonium thioglycolate odor remained. This test was conducted with 20people who used the shampoo of Example 15 and with 20 who did not. Noneof the people who used the shampoo of Example 15 noticed any chemicalodor, whereas all of the people who did not use this shampoo noticed aresidual chemical odor.

Examples 16 to 29 Sshampoo

Other than changing the deodorant in Example 15 to the deodorants ofExamples 1 to 14, the shampoos of Examples 16 to 29 were manufactured inthe same manner [as in Example 15]. The products were evaluated in thesame manner as in Example 15, whereupon no residual odor was detected,and good results were obtained in every case.

Example 30 Treatment Agent

Head hair treatment ingredients wt % quaternary copolymer ofvinylpyrrolidone/ 25 dimethylaminoethyl methacrylate ammoniumcetyltrimethyl bromide 10 purified water balance

The above ingredients were mixed and stirred to prepare a deodorant anda treatment base. 2.5 g of the deodorant prepared in Example 15 wasadded to 97.5 g of this treatment agent base to prepare adeodorant-containing treatment agent. This treatment agent was used intreatment following an ordinary permanent treatment (including anammonium thioglycolate treatment) and washing of the head hair. The sameorganoleptic test as in Example 15 was conducted to see if there was anyresidual ammonium thioglycolate odor after the head hair treatment,whereupon no residual odor was detected, and the same good results wereobtained.

INDUSTRIAL APPLICABILITY

The deodorant of the present invention causes minimal irritation orother adverse effects to the skin or head hair of humans, and has aparticularly outstanding effect in the removal of an ammonia odor fromhead hair that has undergone a permanent treatment.

1-2. (canceled)
 3. A deodorant containing copper gluconate as adeodorizing ingredient.
 4. The deodorant according to claim 3, furthercontaining a betaine compound and/or a carbonyl compound.
 5. A head hairwashing product containing the deodorant according to claim
 3. 6. A headhair treatment method, wherein the head hair is first given a permanentwave, and then washed using the head hair washing product according toclaim
 5. 7. A deodorizing antibacterial substrate, produced by applyingthe deodorant according to claim 3 to the surface and/or the interior ofa fibrous material, granular material, paper, nonwoven cloth, wovencloth, porous substance, or polymer film.
 8. A head hair washing productcontaining the deodorant according to claim
 4. 9. A deodorizingantibacterial substrate, produced by applying the deodorant according toclaim 4 to the surface and/or the interior of a fibrous material,granular material, paper, nonwoven cloth, woven cloth, porous substance,or polymer film.
 10. A deodorizing hair product to counter acidic odorscomprising: a carrier fluid; one of a betaine compound, carbonylcompound and a maleic anhydride hydride copolymer; and a divalent metalcompound selected from a metal oxide, inorganic metal salt and anorganic acid metal salt.
 11. The deodorizing hair product of claim 10wherein the divalent metal compound is copper gluconate.
 12. Thedeodorizing hair product of claim 11 wherein the carrier fluid is 2% to50% by weight of the product and the copper gluconate is approximately4% to 5% by weight.
 13. The deodorizing hair product of claim 12 whereinapproximately 10% by weight of2-alkyl-N-carboxymethyl-N-hydroxyethy-limidazolinium betaine isprovided.
 14. The deodorizing hair product of claim 12 further includingshampoo ingredients constituting a majority percentage by weight.